Producing nitrogen and hydrogen mixtures



Patented Feb. 16, 1932 i Ui ur Dfs AT s.

PA ENT fOFFICE EADPH D. 'DoDGEQo E oHAEDEsToNQWEST VIRGINIA, Assreivoa, 'ZBY MESNE ASSIGN- ;-MENTS,I TO DU roET DE NEMOURS & COMPANY, WILMINGTON, DELAWARE,

A ooEro AmoN 0E, DELAWARE Eton tome nI'rEoGEN NDQEYDEQGEN MIXTURES No Drawing. Original application filed April 29 iosofseriai in; 448,424. Divided and this application I filed January 21, 1931. Serial No. 510,285. I I

I This invention relates to the production of gaseous mixtures of nitrogen and hydrogen and more particularly to the production of such' mixtures by the'catalytic decomposit on ofammonia, as set forth in my'co-pending application, Ser; No. 448,424, filed Apnl 29, 1930, f which the present application is a division." I I It is known that ammonia can be decomposed into its elements, nitrogen and hydrogen,by subjecting it at anelevated temperature to contacflwith iron. This method-of producing nitrogen and hydrogen" jis'fused with advantage where suchfgas'eous mixtures are iequired for the testing of the efficiency.

of catalysts for "the synthesis of ammonia from its elements. Moreover, when employing synthetic ammonia as the raw mater al, this is a convenient way of readily obtain ng hydrogen of a high degree of purity wh ch may advantageously be employed under circumstances such that the presence of the relatively inert nitrogen is of little disadvantage.

Iron alone exhibits, some activety as a catalyst for the thermal decomposition of ammonia but when employed for any prolonged period at such elevated temperatures, say 500 to 700 C. for example, as are desirable for the effective conduct of the reaction, this material becomes owdered and sintered in such a way as to obstruct the passage of gas through the reaction tube. If, therefore, the decomposition of ammonia is to be effected continuously over a long period of time, it is necessary at rather frequent intervals to replace the iron with fresh material.

It is the object of the present invention to provide an improved process for producing gaseous mixtures of nitrogen and hydrogen by the thermal decomposition of ammonia, the process being characterized by the employment of improved catalysts possessing a high degree of activity and capable of use for long periods of time Without disintegration.

Other objects and advantages of the invention will be apparent as it is better understood by reference to the following specification in which its details and preferred embodiments are described.

According to the present invention improved results are obtained in the production of gaseous mixtures of nitrogen and hydrogen by thermal decomposition of ammonia by combining a catalyst containing iron together with one or-more oxides of the elemerits comprising the groups aluminum, zirconium, chromium, magnesiumand calcium. Byemploying catalysts of this composition itis possible to effect the decomposition of ammonia more rapidly and at a lower temperature than-with iron'alone.

Although various methods may-be used in the preparation of the catalyst and other ingredients' than those named above may also be included if desired, I have found that for the best results the catalyst should be substantially free from'elements of the alkali metal group or compounds thereof. For, although the alkai metals and their compounds are frequently used with advantage in catalytic compositions and in fact, due to the methods and the raw materials commonlyemployed in catalyst manufacture one-or more of these elements are likely to be present, my experience has shown that it'is advisable to take precautions to avoid the presence of alkali metals in'the catalyst. In other words, it is preferred to avoid using such methods of preparation as would involve, for instance, the addition of any of the catalyst ingredients in the form of an alkali metal salt or if such catalyst be employed, to take steps toeliminate the alkali metal from the catalystbefore' it-is used in the decomposition of ammonia. f The presence of alkali metal in the catalyst tends to decrease the life thereof, apparently-by sintering and fusing in such a way as to obstruct "the free flow of gas through the body of contact material.

The catalysts herein described and methods for the preparation of which are set forth in the'following examplesare more active-and generally satisfactory in the thermal decomposition of ammonia than iron alone. For example, I have carried on the decomposition of ammonia'fora s long as 500 hours vviithout appreciable deterioration of the cataystH I I I I While various methods 'of preparing the oxide.

catalyst may be employed and the conditions under which'they are used in decomposing ammonia may be varied within wide limits, the following examples are given to illus?- trate the manner of practicing the invention.

Example 1.Mix a 10% solution of ferric sulphate with an equal volume of 10% solution 'ofammonium 'chromate' and then add ammonium hydroxide to complete precipitation. Filter the precipitate, wash free from sulphates and dry. Form vthe dried material into briquets of "suitable size and subject these to reduction bymeans Oihydrogen at a 1. The'pi'dcess of producing a m1xture of a temperature within the range of 300 to 550 C. In employing this catalyst in the thermal decomposition of ammonia it is disposed in a nickel or nichrome tube surrounded by an electrical heater. Vhen ammonia gas is passed over this catalyst at a temperature within the range of 600 to, 700 O. the ammonia is decomposed into its elements and by suitably adjusting the .rate of'iiowv an eflicient conversion of ammonia to nitrogen and hydrogen may be obtained. Any undecomposed ammonia may-be removed from the gaseous products ,byone of the known ways, as, for example, by absorption in water or an acid.. 'EwampZe2.-A catalyst adapted for use in the manner indicated under Example 1 may be prepared by. adding approximately 3% by weight of magnesiiun oxide .and 3% by weight of aluminum oxide to pure ferroso ferric oxide, the percentages being based on the total catalytic material calculated as Melt the oxide mixture, :allow it to cool and crush and screen it to suitable size. The catalyst is subjected to reduction before use.

Example 3.The catalyst described in Ex- 1 ample 1 may be replaced by one prepared by c oxide with 2% by fusing ferroso ferri weight of zirconium oxide. The molten mixture is allowed tocool, crushed,escreened to suitable size and then reduced.

No explanation or theory is .oifered as to any changes in physical form or chemical these temperatures. The reaction can actually be initlated and carried on at lower temperatures, but for efiicient operation of the process I prefer to emPl ythee1ey ated temperatures namedfiHigher. temperatures may also be employed but, generally speaking, with some deterioration in the physical form of the catalysti -Various changes may be'made-in the method describedwithout-departing from the invention or sacrificingany of the advantages thereof. I claim: I)

nitrogen'an'd hydrogen which comprises contacting gaseous ammonia at an elevated tem- Ps a u i chromium oxide. l, ,2. The processof producing a mixture of nitrogen and hydrogen which comprises contaeting gaseous ammonia atv a temperature within the range of 600-700? C. with a catalyst comprising iron and chromium oxide. The. processof producinga mixture of nitrogen and hydrogen which-comprises contacting gaseous. ammonia at anelevatedtemperature,wi thg a catalyst-consisting of iron and chromium oxide, said catalyst being substantially free from alkali metal.

Intestimony whereof, I aflix my signature. f L. DODGE.

composition that may occur in the catalyst in the course of itsreduction or'during actual use. The term catalyst as employed in the claimsIis intended, therefore, to includethe contact mass as prepared as well as any modified form in which it may exist during the reaction. It should also be understood that, since it is generally recognized that the activity of substances as catalysts is'a function of the chemical elements contained therein rather than of the particular type of com-v pound employed, the term oxide as employed herein is to be considered as including oxides as such or as they may be present in chem-. ical combination with other elements. I

1 -While the temperature range of 600-700"- C. indicated-in theforegoing examples represents the preferred temperature range, the inventionis not limited to. the utilization of h a catalyst comprising iron and 

